JP2000095865A - Production of organosilicon resin and polyurethane foam using the resin obtained by the same production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide methods for producing polyurethane foam having properties such as excellent dimensional stability and utilizable to a spray foaming also by adding an organosilicon resin comfortably dispersing in a resin premix and having a high hydrophobicity and low reactivity to the resin premix and increasing its storage stability, and for producing an organosilicon resin comfortably usable to the method. SOLUTION: In producing a polyurethane foam by foaming and hardening a polyurethane foam composition containing a resin premix containing polyol, water, a catalyst and a surfactant and a polyisocyanate, an organosilicon resin containing R13SiO1/2 unit (R1 is a 1-6C monofunctional hydrocarbon group), R2SiO3/2 unit (R2 is a 1-20C monofunctional hydrocarbon group) and SiO4/2 unit as constituting units is added to the resin premix in a solution state.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an organosilicon resin and a method for producing a polyurethane foam using the organosilicon resin obtained by the production method, and more particularly to a method for improving dimensional stability by improving the storage stability of a resin premix. The present invention relates to a method for producing a polyurethane foam from which a polyurethane foam having excellent properties such as properties can be obtained.

[0002]

2. Description of the Related Art Polyurethane foams are generally polyurethane foam compositions containing a polyol or polyisocyanate, water or carboxylic acid as a blowing agent, an alkali catalyst such as an amine as a catalyst, and a surfactant as a foam stabilizer (before use or storage). The inside is usually produced by foaming and curing a resin premix in which a polyol, a foaming agent, a catalyst and a foam stabilizer are mixed, and a polyisocyanate), but in this production method, For the purpose of improving the appearance and other physical properties of the foam, it has been proposed to use a resin premix with an additive incompatible with the resin premix. This additive is useful for improving the dimensional stability of the obtained polyurethane foam, especially in a composition using water as a foaming agent. As an additive of this type, carbon black (JP-A-55-13512) is used for producing a semi-rigid polyurethane foam.
8), and powdery or fibrous potassium titanate (JP-A-56-1)
4535), R ₃ SiO _1/2 units (where R ³ represents the same or different monovalent hydrocarbon groups having 1 to 6 carbon atoms), and organosilicon compounds having SiO ₂ units as constituent units are proposed. Have been.

[0003]

However, since these additives are incompatible with the resin premix, they are separated from the resin premix over time or deteriorated by an alkali catalyst in the resin premix, and There is a big problem that characteristics such as improvement of dimensional stability cannot be exhibited. Therefore, conventionally, it is necessary to stir and uniformly mix and disperse the resin premix before use, that is, before mixing and reacting (foaming and curing) with the isocyanate. There was also a problem that the foaming means was limited. In order to solve these problems, it has been desired to develop an additive which is compatible with the resin premix, is therefore well dispersed in the resin premix, and has high hydrophobicity and low reactivity.

Accordingly, an object of the present invention is to solve the above problems in the production of a polyurethane foam, and to add an organosilicon resin which is well dispersed in a resin premix and has high hydrophobicity and low reactivity to the resin premix. Thus, by improving the storage stability, a polyurethane foam having excellent dimensional stability and other properties can be produced, and a polyurethane foam production method which can be used for spray foaming, and is preferably used in the method. To provide a method for producing an organosilicon resin.

[0005]

According to the present invention, R¹ _ThreeSiO
_1/2Unit (however, R¹Is the same or different from 1 to 6 carbon atoms
Represents a valent hydrocarbon. ), R^TwoSiO_3/2Unit (however, R^Two
Represents the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms.
You. ) And SiO_4/2Organosilicon with units as constituent units
It provides a method for manufacturing resin, and this manufacturing method
Formula (I): Si (OR^Three)_Four (I)  (However, R^ThreeAre the same or different monovalent carbons with 1 to 6 carbon atoms
Represents a hydrogen group, preferably an alkyl group having 1 to 4 carbon atoms. )
A silane compound or a hydrolyzate thereof represented by the general formula
(II): R^TwoSi (OR^Four)_Three (II)  (However, R^TwoAre the same or different, having 1 to 20 carbon atoms, preferably
Represents a monovalent hydrocarbon group of 1 to 10;^FourAre the same or different
A monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms
Represents an alkyl group. ) Or a silane compound represented by
The hydrolyzate thereof, and the general formula (III): R¹ _ThreeSix (III) (where X is -OH group, -OSiR¹ _ThreeGroup or hydrolysis
A functional group;¹Are the same or different monovalent C1-6
Represents a hydrocarbon group. A) a mixture of silane compounds represented by
Of equilibrium reaction with acid, water is added to the equilibrium reaction product
A step of performing a hydrolysis reaction by adding, and a hydrolysis reaction
Including the step of adding alkaline water to the product to perform a condensation reaction.
It is characterized by the following.

The present invention also provides a method for producing a polyurethane foam by foaming and curing a polyurethane foam composition containing a resin premix containing a polyol, water, a catalyst and a surfactant, and a polyisocyanate. A method for producing a polyurethane foam, comprising adding the organosilicon resin obtained by the above-mentioned production method in a solution state.

[0007] The present inventors have conducted various studies on additives to be added to the resin premix in the production of the polyurethane foam, and found that the organic silicon resin obtained by the above-described method for producing an organic silicon resin is compatible with the resin premix. It is soluble, disperses well, and has high hydrophobicity and low reactivity, so it can be stably stored for a long time without being separated from the resin premix over time or deteriorating with an alkali catalyst. Also, when a resin premix to which an organosilicon resin having the above-mentioned characteristics is added is used, a polyurethane foam having characteristics such as excellent dimensional stability can be obtained, and it can be used for spray foaming. Completed the invention.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

In the present invention, the polyurethane foam is produced by foaming and curing a polyurethane foam composition containing a resin premix containing a polyol, water, a catalyst and a surfactant, and a polyisocyanate. The feature of this production method is that a resin premix to which the organic silicon resin obtained by the above production method is added in a solution state is used.

The organic silicon resin can be manufactured as follows. That is, first, a silane compound represented by the general formula (I) or a hydrolyzate thereof, a silane compound represented by the general formula (II) or a hydrolyzate thereof, and a silane compound represented by the general formula (III) A mixture (hereinafter, referred to as a mixture raw material) is subjected to an equilibrium reaction with an acid, and water is added to the obtained equilibrium reaction product to perform a hydrolysis reaction. Then, alkaline water is added to the hydrolysis reaction product. It is produced by performing a condensation reaction. The equilibration reaction, hydrolysis reaction and condensation reaction are usually performed in an organic solvent.

Specific examples of the mixture raw material used in the equilibration reaction step are as follows. Specific examples of the silane compound represented by the general formula (I) include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.
Specific examples of the hydrolyzate of the silane compound represented by the general formula (I) include methyl silicate and ethyl silicate. These silane compounds or hydrolysates thereof can be used alone or in combination of two or more. Further, the silane compound and a hydrolyzate thereof may be used as a mixture.

Specific examples of the silane compound represented by the general formula (II) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane,
alkoxysilanes such as n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, and hexyltrimethoxysilane; and hydrolyzates thereof. May be used. These silane compounds or hydrolysates thereof can be used alone or in combination of two or more. Among them, a silane compound represented by the general formula (II) is a compound in which R ² is a methyl group and a compound in which R ² is It is preferably a mixture with a compound which is a monovalent hydrocarbon group having 3 to 10 carbon atoms. Further, the silane compound and a hydrolyzate thereof may be used as a mixture.

Specific examples of the silane compound represented by the general formula (III) include silanol compounds such as trimethylsilanol and triethylsilanol; chlorosilanes such as trimethylchlorosilane and triethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane and trimethylethoxysilane; Examples include aminosilanes such as trimethylsilyldimethylamine and trimethylsilyldiethylamine, acyloxysilanes such as trimethylacetoxysilane, and disiloxanes such as hexamethyldisiloxane. Further, these hydrolysates may be used. These silane compounds or hydrolysates thereof can be used alone or in combination of two or more. Further, the silane compound and a hydrolyzate thereof may be used as a mixture.

The content of the silane compound represented by the general formula (II) or the hydrolyzate thereof in the raw material of the mixture is determined based on the content of the SiO _4/2 unit in the silane compound represented by the general formula (I) or the hydrolyzate thereof. The amount is preferably 0.5 to 1.0 equivalent, particularly 0.7 to 0.9 equivalent, in units of R ² SiO _{3/2 based on the} number of moles. Further, of these, R ² SiO _3/2 units (where R ² =
Hexyl group) is preferably 0.05 to 0.3 equivalent. Further, the content of the silane compound represented by the general formula (III) in the raw material of the mixture is defined as R ^{1 based on the} number of moles of SiO ₂ units in the silane compound represented by the general formula (I) or a hydrolyzate thereof. ₃ 0.5 to 1.5 equivalents in SiO _1/2 unit, especially 0.8 to 0.9
Equivalent amounts are preferred.

Specific examples of the acid used in the equilibration reaction step include sulfonic acids such as methanesulfonic acid and sulfuric acid. The amount of the acid added is preferably 0.5 to 2% by weight, particularly preferably 1 to 1.5% by weight, based on the weight of the mixture raw material used.

The organic solvent used in the equilibration reaction step may be a mixture raw material (ie, a compound of the general formula (I) and / or a hydrolyzate thereof, a compound of the general formula (II) and / or a hydrolyzate thereof, And any compound that dissolves the equilibrium reaction product and the equilibration reaction product and is compatible with water (hereinafter referred to as a hydrophilic organic solvent), such as methyl alcohol and ethyl alcohol. , Alcohols such as propyl alcohol, isopropyl alcohol, and butyl alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and cellosolve acetate; ketones such as acetone and methyl ethyl ketone; ethers such as dioxane and tetrahydrofuran; preferably alcohols Is mentioned.

The amount of water added in the hydrolysis reaction step is as follows:
The amount is preferably 0.5 to 1.5 equivalents, and more preferably 0.8 to 1.0 equivalent, relative to the number of moles of a hydrolyzable group such as an alkoxy group contained in the used mixture raw material.

The organic solvent used in the hydrolysis reaction step can be used without particular limitation as long as it dissolves the equilibration reaction product and the hydrolysis reaction product and is compatible with water. Examples include the hydrophilic organic solvents exemplified in the reaction step.

Specific examples of the alkaline water used in the condensation reaction step include aqueous potassium hydroxide, aqueous sodium hydroxide, aqueous ammonia, aqueous dimethylamine, and aqueous diethylamine. The amount of alkaline water added is 1.0 to 1.5 equivalents based on the number of moles of the acid used in the equilibration reaction step,
Particularly, 1.05 to 1.4 equivalents are preferable.

The organic solvent used for the condensation reaction can be used without particular limitation as long as it can dissolve the hydrolysis reaction product and the condensation reaction product (that is, the organosilicon resin) and is not compatible with water. Include aliphatic hydrocarbons such as hexane, cyclohexane, and isoparaffin; benzene,
Examples thereof include aromatic hydrocarbons such as toluene and xylene, and preferably include aromatic hydrocarbons.

The organic silicon resin obtained as described above includes unreactive siloxanes such as decamethylcyclopentasiloxane and octamethylcyclotetrasiloxane.
Alternatively, the organic silicon resin is dissolved in an organic solvent such as a hydrocarbon capable of dissolving the above-mentioned organic silicon resin, is compatible with the resin premix, is well dispersed, and has high hydrophobicity and low reactivity. This organic silicon resin is added to the premix after being dissolved in the above organic solvent. The amount of the organosilicon resin added to the resin premix is preferably 0.01 to 20 parts by weight, more preferably 0.1 to 5 parts by weight, particularly preferably 0.5 part by weight, per 100 parts by weight of the polyol.

The polyol, the catalyst and the surfactant other than the organosilicon resin constituting the resin premix; and the polyisocyanate mixed with the resin premix include:
Any of them may be those usually used for producing polyurethane foam. That is, examples of the polyol include polyether polyols such as polyethylene glycol and polypropylene glycol; and hydroxyl group-containing compounds such as polyester, acrylic polyol, castor oil derivatives, and tall oil derivatives.

Examples of the catalyst include amine compounds such as tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, triethylamine and triethylenediamine, and tin catalysts such as stannous chloride and dibutyltin laurate. The content of the catalyst in the resin premix was 0.00% by weight based on the amount of the polyol.
The amount is preferably from 01 to 0.1 times, particularly preferably from 0.001 to 0.01 times.

The surfactant (foam stabilizer) is not particularly limited, but is preferably, for example, a polyethersiloxane such as a dimethylpolysiloxane-polyoxyethylene-polyoxypropylene copolymer. The content of the surfactant in the resin premix is preferably 0.0001 to 0.1 times, more preferably 0.001 to 0.05 times the weight of the polyol. Further, the content of water in the resin premix is 0.001 to 0.5 times the weight of the polyol with respect to the amount of the polyol, especially 0.1.
The amount is preferably from 01 to 0.3 times. In addition, a flame retardant, a filler, and the like can be added to the resin premix as long as the effects of the present invention are not impaired.

Examples of the polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, meta-xylylene diisocyanate, xylylene diisocyanate, and the like.
Derivatives thereof, hydrogenated products and the like can be mentioned. The amount of the polyisocyanate used in the composition is preferably such that the isocyanate index becomes 50 to 150, particularly preferably 80 to 110.

In the present invention, foaming and curing of the polyurethane foam composition are carried out by mixing the resin premix to which the above-mentioned organosilicon resin is added with polyisocyanate. The foaming means may be the same as that of ordinary urethane foam, and low-pressure foaming and high-pressure foaming are possible, and free foaming, spray foaming, flossing, non-flossing, and the like can be used.

[0027]

The present invention will be described in detail below with reference to examples and comparative examples. All parts are parts by weight. Example 1 In a 1-liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 73.6 g of hexamethyldisiloxane and hexyltrimethoxysilane (trade name K manufactured by Shin-Etsu Chemical Co., Ltd.)
16.5 g of BM3063), 96.7 g of a hydrolyzate of methyltrimethoxysilane (trade name KC89R manufactured by Shin-Etsu Chemical Co., Ltd.),
150 g of ethyl polysilicate (trade name Keisan 40 manufactured by Colcoat Co., Ltd.), 4.21 g of methanesulfonic acid, and 37.4 g of isopropyl alcohol were charged and mixed. Add this solution to 40
After the equilibration reaction was carried out by holding at 2 ° C. for 2 hours, 68.3 g of water was added, and the hydrolysis reaction was carried out at 70 ° C. for 2 hours. After 111 g of xylene was added to the reaction product, 7.6 g of a 50% aqueous potassium hydroxide solution was added, the mixture was kept at 72 to 78 ° C. for 8 hours, then the alcohol was distilled off, and the mixture was further kept at 135 to 142 ° C. for 10 hours. To carry out a condensation reaction. After adding 264 g of xylene to the reaction product, the reaction product was washed with water until it became neutral. The solvent of the organic layer was stripped to obtain 70 g of an organic silicon resin.

100 parts of a polyol (polyol actocol GR-46, trade name, manufactured by Takeda Pharmaceutical Co., Ltd.), and tetramethylhexamethylenediamine (TMHDA) as a catalyst
1.7 parts, water 6.2 parts as a foaming agent, foam stabilizer as a surfactant: dimethylpolysiloxane-polyoxyethylene-
A resin premix was prepared by adding 1 part of a polyoxypropylene copolymer (trade name: F-373, manufactured by Shin-Etsu Chemical Co., Ltd.) and a solution prepared by dissolving 0.5 part of the above organic silicon resin in 0.5 part of decamethylcyclopentasiloxane. Prepared. Even when the resin premix was left at 50 ° C. for 3 days, no sediment was observed, and the resin premix was stable.

The resin premix after aging is mixed with a polyisocyanate (Isocyanate Sumidum 444V-trade name, manufactured by Sumitomo Bayer Urethane Co., Ltd.).
20) was added so that the isocyanate index became 110, and the mixture was foamed and cured to obtain a rigid urethane foam. The density of the urethane foam was measured, and the appearance after the urethane foam was allowed to stand under high temperature and high humidity (70 ° C., 95% RH) for 2 days was examined. The results are shown in Table 1. As can be seen from this table, this urethane foam had low density and good dimensional stability. As described above, the resin premix did not cause separation or deterioration of the organic silicon resin, and the desired characteristics were obtained.

Examples 2 to 10 Amount of hexamethyldisiloxane, amount of KBM 3063, amount of KC89R
An organosilicon resin was prepared in the same manner as in Example 1 except that the amount and the amount of a 50% aqueous potassium hydroxide solution were as shown in Table 1. Further, a resin premix was prepared using the resin premix in the same manner as in Example 1, and its storage stability was examined. A polyurethane foam was produced using these resin premixes, and the foam characteristics were examined. Table showing the results
Shown in 1.

Comparative Examples 1 to 3 Organosilicon resins were prepared in the same manner as in Example 1 except that the amounts of hexamethyldisiloxane and 50% aqueous potassium hydroxide were changed as shown in Table 1. Further, a resin premix was prepared using the resin premix in the same manner as in Example 1, and the storage stability was examined. A polyurethane foam was produced using these resin premixes, and the foam characteristics were examined. Table 1 shows the results.

[0032]

[Table 1] Note actual: embodiment, the ratio: Comparative Example M units: R ¹ ₃ SiO _1/2 units, T ³⁰⁶³ unit = R ² SiO _3/2 units (R ² = hexyl) T ¹³ Unit: R ² SiO _{3 / 2} unit Q unit: SiO ₂ unit

[0033]

The organosilicon resin obtained by the production method of the present invention is suitable for producing polyurethane foam. According to the production method of polyurethane foam using this organosilicon resin, the organosilicon resin is well dispersed in the resin premix. Since the resin premix to which the organic silicon resin having high hydrophobicity and low reactivity is added is used, the storage stability of the resin premix is improved, and the additive (organic silicon resin) can be used even when stored for a long time.
This eliminates the need for agitation during use, and thus eliminates the need for stirring during use, thus providing a polyurethane foam having the desired properties such as excellent dimensional stability, and has the effect of being usable for spray foaming. Play.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Mitsuo Asai 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture F-term in the Silicon Electronics Research Laboratory, Shin-Etsu Chemical Co., Ltd. 4J034 DA01 DB03 DF01 DG03 DG04 DP18 EA12 EA13 HA07 HC03 HC12 HC52 HC64 HC67 HC71 HC73 MA24 NA03 NA05 QC01 4J035 BA15 CA01N EA01 EB02 LA05 LB20

Claims (4)

[Claims] 1. A compound of the general formula (I): Si (OR^Three)_Four (I)  (However, R^ThreeAre the same or different monovalent carbons with 1 to 6 carbon atoms
Represents a hydrogen group. ) Or a silane compound represented by
Hydrolyzate, general formula (II): R^TwoSi (OR^Four)_Three (II)  (However, R^TwoAre the same or different monovalent carbons with 1 to 20 carbon atoms
Represents a hydrogen group, R^FourIs the same or different from 1 to 6 carbon atoms
Represents a valent hydrocarbon group. ) Or a silane compound represented by
The hydrolyzate thereof, and the general formula (III): R¹ _ThreeSix (III) (where X is -OH group, -OSiR¹ _ThreeGroup or hydrolysis
A functional group;¹Are the same or different monovalent C1-6
Represents a hydrocarbon group. A) a mixture of silane compounds represented by
To equilibrate the product with an acid.
And adding alkaline water to the hydrolysis reaction product
R comprising a step of performing a condensation reaction.¹ _ThreeSiO
_1/2Unit (however, R¹Is the same or different from 1 to 6 carbon atoms
Represents a valent hydrocarbon. ), R^TwoSiO_3/2Unit (however, R^Two
Represents the same or different monovalent hydrocarbon groups having 1 to 20 carbon atoms.
You. ) And SiO_4/2Organosilicon with units as constituent units
Method of manufacturing resin. 2. A silane compound represented by the general formula (II):
Production method of the organosilicon resin of claim 1 wherein the mixture of compound and R ² R ² is a methyl group with a compound which is a monovalent hydrocarbon group having 3 to 10 carbon atoms. 3. The content of the silane compound represented by the general formula (II) or the hydrolyzate thereof is determined by the number of moles of SiO _4/2 units in the silane compound represented by the general formula (I) or the hydrolyzate thereof. ^{3. The} method for producing an organosilicon resin according to claim 1, wherein the amount is 0.5 to 1.0 equivalent in R ² SiO _3/2 units. 4. A method for producing a polyurethane foam by foaming and curing a polyurethane foam composition containing a resin premix containing a polyol, water, a catalyst and a surfactant and a polyisocyanate, as the resin premix. A method for producing a polyurethane foam, comprising adding the organosilicon resin obtained by the production method according to any one of Items 1 to 3 in the form of a solution.